JP2015108131A - Fluorine-containing polymer and treatment agent - Google Patents

Fluorine-containing polymer and treatment agent Download PDF

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JP2015108131A
JP2015108131A JP2014215288A JP2014215288A JP2015108131A JP 2015108131 A JP2015108131 A JP 2015108131A JP 2014215288 A JP2014215288 A JP 2014215288A JP 2014215288 A JP2014215288 A JP 2014215288A JP 2015108131 A JP2015108131 A JP 2015108131A
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fluorine
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monomer
acrylate
atom
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JP5862745B2 (en
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留美 川部
Rumi Kawabe
留美 川部
良輔 原
Ryosuke Hara
良輔 原
恭平 澤木
Kyohei Sawaki
恭平 澤木
育男 山本
Ikuo Yamamoto
育男 山本
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Daikin Industries Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment agent that imparts excellent water repellency, oil repellency, soil resistance, and soil release property to a base material.SOLUTION: A fluorine-containing polymer has: (a) a repeating unit derived from a fluorine-containing monomer which is an acrylate ester monomer substituted with an univalent organic group or a halogen atom at a α-position and has a fluoroalkyl group; (b) a repeating unit derived from a non-fluorine monomer which is an alkyl acrylate having a 6-13C alkyl group; and (c) a repeating unit derived from a non-fluorine (meth)acrylate monomer having a cyclic hydrocarbon group.

Description

本発明は、含フッ素重合体、および該含フッ素重合体を含んでなる処理剤に関する。本発明の処理剤は、撥水撥油性、特に撥水撥油性の耐久性に優れている。   The present invention relates to a fluorinated polymer and a treating agent comprising the fluorinated polymer. The treatment agent of the present invention is excellent in durability of water / oil repellency, particularly water / oil repellency.

従来、含フッ素重合体を使用する種々の表面処理剤が、例えば、国際公開2002/083809公報（特許文献１）、国際公開2009/008512公報（特許文献２）および国際公開2004/096939公報（特許文献３）において提案されている。特許文献１および特許文献２は、ステアリルアクリレートなどの炭素数が１５以上のアルキル基を有する（メタ）アクリレート単量体を使用する含フッ素重合体を含んでなる撥水撥油剤組成物を開示している。
しかしながら、特許文献１および特許文献２の撥水撥油剤組成物は、撥水撥油性が不充分であり、特に、撥水撥油性の耐久性が不充分であった。 Conventionally, various surface treatment agents using a fluorine-containing polymer are, for example, International Publication 2002/083809 (Patent Document 1), International Publication 2009/008512 (Patent Document 2) and International Publication 2004/096939 (Patent Document). It is proposed in the literature 3). Patent Document 1 and Patent Document 2 disclose a water / oil repellent composition comprising a fluoropolymer using a (meth) acrylate monomer having an alkyl group having 15 or more carbon atoms such as stearyl acrylate. ing.
However, the water / oil repellent compositions of Patent Document 1 and Patent Document 2 have insufficient water / oil repellency, and in particular, have insufficient water / oil repellency durability.

また、従来の一般的な水性分散液を希釈して調合される撥水撥油剤加工浴では、処理される生地が入るときに受ける機械的衝撃により分散液が壊れ、エマルション粒子が凝集、沈降が起こったりして、撥ロールにポリマーが付着して生地汚れとなる、ロール汚れとなるなどのトラブルがしばしば発生していた。ロールにポリマーが付着する問題については、ポリマーの粘着性が高いほど問題が起こりやすい。   In addition, in a conventional water / oil repellent processing bath prepared by diluting a general aqueous dispersion, the dispersion breaks due to mechanical impact when the fabric to be treated enters, and emulsion particles aggregate and settle. In many cases, problems such as the occurrence of a soiling of the fabric due to the polymer adhering to the repellent roll and the soiling of the roll have occurred. Regarding the problem of the polymer adhering to the roll, the higher the polymer tackiness, the more likely the problem occurs.

国際公開2002/083809公報International Publication 2002/083809 国際公開2009/008512公報International Publication 2009/008512 国際公開2004/096939公報International Publication 2004/096939

本発明の目的は、繊維織物等の基材に対して、優れた撥水性、撥油性、防汚性および汚れ脱離性を付与する処理剤（特に、表面処理剤）を提供することにある。   An object of the present invention is to provide a treatment agent (particularly, a surface treatment agent) that imparts excellent water repellency, oil repellency, antifouling properties, and dirt release properties to substrates such as textile fabrics. .

この課題を解決するために、以下の発明に至った。すなわち、本発明は、
（ａ）α位が一価の有機基またはハロゲン原子で置換されているアクリレートエステル単量体である、フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位、
（ｂ）アルキル基の炭素数が６〜１３であるアルキルアクリレートである非フッ素単量体から誘導された繰り返し単位、および
（ｃ）環状炭化水素基を有する非フッ素（メタ）アクリレート単量体から誘導された繰り返し単位を有してなる含フッ素重合体に関する。 In order to solve this problem, the inventors have reached the following invention. That is, the present invention
(A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group, which is an acrylate ester monomer substituted at the α-position with a monovalent organic group or a halogen atom,
(B) a repeating unit derived from a non-fluorine monomer which is an alkyl acrylate having 6 to 13 carbon atoms in the alkyl group, and (c) a non-fluorine (meth) acrylate monomer having a cyclic hydrocarbon group The present invention relates to a fluoropolymer having derived repeating units.

本発明によれば、優れた撥水性、撥油性、防汚性および汚れ脱離性、特に、撥水撥油性の優れた耐久性が得られる。本発明の処理剤は、処理剤における含フッ素重合体が低濃度であっても、優れた性能（例えば、撥水撥油性）を与える。本発明の処理剤は、処理剤の優れた安定性、例えば加工安定性および他の薬剤との併用安定性を有しており、過酷な条件での撥水性、例えば強撥水性を与える。処理された基材は、ラビングされても高い性能（例えば、撥水撥油性）を有しており、高い耐摩耗性を有する。さらに、本発明の処理剤は、加工処理において、ロールへのポリマー付着性防止に優れる。   According to the present invention, excellent water repellency, oil repellency, antifouling property and dirt detachability, in particular, excellent durability with excellent water and oil repellency can be obtained. The treatment agent of the present invention provides excellent performance (for example, water and oil repellency) even when the concentration of the fluoropolymer in the treatment agent is low. The treatment agent of the present invention has excellent stability of the treatment agent, such as processing stability and stability in combination with other agents, and provides water repellency under severe conditions, such as strong water repellency. The treated substrate has high performance (for example, water and oil repellency) even when rubbed, and has high wear resistance. Furthermore, the treatment agent of the present invention is excellent in preventing polymer adhesion to a roll during processing.

本発明において、含フッ素重合体の繰り返し単位を構成する単量体として、含フッ素単量体（ａ）、非フッ素アルキルアクリレート単量体（ｂ）および環状炭化水素基を有する非フッ素アクリレート単量体（ｃ）を使用する。
必要により、含フッ素重合体は、単量体（ａ）、（ｂ）および（ｃ）以外の他の単量体（特に、非フッ素単量体）から誘導された繰り返し単位、例えば、
（ｄ）ハロゲン化オレフィン単量体から誘導された繰り返し単位、および/または
（ｅ）単量体（ｂ）、（ｃ）および（ｄ）以外の非フッ素単量体から誘導された繰り返し単位
を有してよい。
非フッ素単量体（ｅ）の例は、（ｅ１）非フッ素架橋性単量体である。 In the present invention, the monomer constituting the repeating unit of the fluorine-containing polymer includes a fluorine-containing monomer (a), a non-fluorine alkyl acrylate monomer (b), and a non-fluorine acrylate monomer having a cyclic hydrocarbon group. Use body (c).
If necessary, the fluoropolymer may be a repeating unit derived from a monomer other than the monomers (a), (b) and (c) (particularly a non-fluorine monomer), for example,
(D) a repeating unit derived from a halogenated olefin monomer, and / or (e) a repeating unit derived from a non-fluorine monomer other than the monomers (b), (c) and (d) You may have.
An example of the non-fluorine monomer (e) is (e1) a non-fluorine crosslinkable monomer.

本発明において、含フッ素重合体の繰り返し単位を構成する単量体の組み合わせは、例えば、次のとおりである。
（１）単量体（ａ）＋単量体（ｂ）＋単量体（ｃ）
（２）単量体（ａ）＋単量体（ｂ）＋単量体（ｃ）＋単量体（ｄ）
（３）単量体（ａ）＋単量体（ｂ）＋単量体（ｃ）＋単量体（ｅ）
（例えば、単量体（ａ）＋単量体（ｂ）＋単量体（ｃ）＋単量体（ｅ１））
（４）単量体（ａ）＋単量体（ｂ）＋単量体（ｃ）＋単量体（ｄ）＋単量体（ｅ）
（例えば、単量体（ａ）＋単量体（ｂ）＋単量体（ｃ）＋単量体（ｄ）＋単量体（ｅ１））
含フッ素重合体の繰り返し単位を構成する単量体の組み合わせは、組み合わせ（１）、（２）または（３）であってもよいが、組み合わせ（４）であることが特に好ましい。 In the present invention, the combination of monomers constituting the repeating unit of the fluoropolymer is, for example, as follows.
(1) Monomer (a) + monomer (b) + monomer (c)
(2) Monomer (a) + monomer (b) + monomer (c) + monomer (d)
(3) Monomer (a) + Monomer (b) + Monomer (c) + Monomer (e)
(For example, monomer (a) + monomer (b) + monomer (c) + monomer (e1))
(4) monomer (a) + monomer (b) + monomer (c) + monomer (d) + monomer (e)
(For example, monomer (a) + monomer (b) + monomer (c) + monomer (d) + monomer (e1))
The combination of monomers constituting the repeating unit of the fluoropolymer may be the combination (1), (2) or (3), but the combination (4) is particularly preferable.

本発明の含フッ素重合体は、撥水撥油剤、防汚剤および汚れ脱離剤の有効成分として使用できる。   The fluoropolymer of the present invention can be used as an active ingredient of a water / oil repellent, an antifouling agent and a soil release agent.

（ａ）含フッ素単量体
含フッ素単量体は、α位が一価の有機基またはハロゲン原子で置換されているアクリレートエステル単量体またはアクリルアミド単量体である。含フッ素単量体のα位の一価の有機基は、メチル基であってもよいが、メチル基でないことが好ましい。
含フッ素単量体は式：
CH2=C(-X)-C(=O)-Y-Z-Rf
［式中、Ｘは、一価の有機基またはハロゲン原子であり、
Y は、-O- または -NH-であり、
Ｚは、直接結合または二価の有機基であり、
Ｒｆは、炭素数１〜２０のフルオロアルキル基である。］
で示される含フッ素単量体である。
Ｚは、例えば、炭素数１〜２０の直鎖状または分岐状脂肪族基（特に、アルキレン基）、例えば、式−（ＣＨ２）ｘ−（式中、ｘは１〜１０である。）で示される基、あるいは、式−Ｒ２（Ｒ１）Ｎ−ＳＯ２−または式−Ｒ２（Ｒ１）Ｎ−ＣＯ−で示される基（式中、Ｒ１は、炭素数１〜１０のアルキル基であり、Ｒ２は、炭素数１〜１０の直鎖アルキレン基または分枝状アルキレン基である。）、あるいは、式−ＣＨ２ＣＨ（ＯＲ３）ＣＨ２−（Ａｒ−Ｏ）p−（式中、Ｒ３は、水素原子、または、炭素数１〜１０のアシル基（例えば、ホルミルまたはアセチルなど）、Ａｒは、置換基を必要により有するアリーレン基、ｐは０または１を表す。）で示される基、あるいは、式−ＣＨ２−Ａｒ−(Ｏ)ｑ−（式中、Ａｒは、置換基を必要により有するアリーレン基、ｑは０または１である。）で示される基、-(CH2)m−SO2−(CH2)n−基 または -(CH2)m−S−(CH2)n−基（但し、mは１〜１０、nは０〜１０、である）であってよい。
Ｘの代表的な具体例は、Ｃｌ、Ｂｒ、Ｉ、Ｆ、ＣＮ、ＣＦ３である。 (A) Fluorinated monomer The fluorinated monomer is an acrylate ester monomer or an acrylamide monomer in which the α-position is substituted with a monovalent organic group or a halogen atom. The monovalent organic group at the α-position of the fluorinated monomer may be a methyl group, but is preferably not a methyl group.
The fluorine-containing monomer has the formula:
CH 2 = C (-X) -C (= O) -YZ-Rf
[Wherein X is a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a C1-C20 fluoroalkyl group. ]
It is a fluorine-containing monomer shown by.
Z is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group), for example, a formula — (CH 2 ) x — (wherein x is 1 to 10). Or a group represented by the formula —R 2 (R 1 ) N—SO 2 — or a formula —R 2 (R 1 ) N—CO— (wherein R 1 has 1 to 10 carbon atoms) Or R 2 is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.) Or a formula —CH 2 CH (OR 3 ) CH 2 — (Ar—O) p- (wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (eg, formyl or acetyl), Ar is an arylene group optionally having a substituent, and p is 0 or 1) . representing a group represented by) or the formula -CH 2 -Ar- (O) q - ( wherein, Ar is An arylene group having necessary a substituent, group q is represented by a 0 or 1), -. (CH 2 ) m -SO 2 - (CH 2) n - group or a - (CH 2) m -S- It may be a (CH 2 ) n — group (where m is 1 to 10 and n is 0 to 10).
Typical examples of X are Cl, Br, I, F, CN, CF 3 .

含フッ素単量体（ａ）は、式：
CH2=C(−X)−C(=O)−Y−Z−Rf （Ｉ）
［式中、Ｘは、炭素数２〜２１の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ1Ｘ2基（但し、Ｘ1およびＸ2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基であり；
Ｙは、−Ｏ−または−ＮＨ−であり；
Ｚは、炭素数１〜１０の脂肪族基、炭素数６〜１８の芳香族基または環状脂肪族基、
-CH2CH2N(R1)SO2−基（但し、R1は炭素数１〜４のアルキル基である。）、
-CH2CH(OZ1)CH2-(Ph-O)p-基（但し、Z1は水素原子またはアセチル基、Phはフェニレン基、ｐは０または１である。）、-(CH2)n-Ph-O-基（但し、Phはフェニレン基、ｎは０〜１０である。）、-(CH2)m−SO2−(CH2)n−基または -(CH2)m−S−(CH2)n−基（但し、mは１〜１０、nは０〜１０である）、
Ｒｆは、炭素数１〜２０の直鎖状または分岐状のフルオロアルキル基である。]
で示されるアクリレートエステルまたはアクリルアミドであることが好ましい。 The fluorine-containing monomer (a) has the formula:
CH 2 = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where X 1 and X 2 are A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, substituted or non-substituted A substituted phenyl group;
Y is —O— or —NH—;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms),
-CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (where Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH 2 ) n -Ph-O-group (where, Ph is a phenylene radical, n is 0~10), -. (CH 2 ) m -SO 2 - (CH 2) n - group or - (CH 2) m -S- (CH 2) n - group (where, m is 1 to 10, n is 0-10),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
An acrylate ester or acrylamide represented by

含フッ素単量体（ａ）は、α位がハロゲン原子などで置換されているアクリレートである。Ｘは、塩素原子であることが好ましい。   The fluorine-containing monomer (a) is an acrylate in which the α-position is substituted with a halogen atom or the like. X is preferably a chlorine atom.

上記式（１）において、Ｒｆ基が、パーフルオロアルキル基であることが好ましい。Ｒｆ基の炭素数は、１〜６、特別には４〜６であることが好ましい。Ｒｆ基の例は、−ＣＦ3、−ＣＦ2ＣＦ3、−ＣＦ2ＣＦ2ＣＦ3、−ＣＦ(ＣＦ3) 2、−ＣＦ2ＣＦ2ＣＦ2ＣＦ3、−ＣＦ2ＣＦ(ＣＦ3)2、−Ｃ(ＣＦ３)3、−(ＣＦ2)4ＣＦ3、−(ＣＦ2)2ＣＦ(ＣＦ3)2、−ＣＦ2Ｃ(ＣＦ3)3、−ＣＦ(ＣＦ3)ＣＦ2ＣＦ2ＣＦ3、−(ＣＦ2)5ＣＦ3、−(ＣＦ2)3ＣＦ(ＣＦ3)2、−(ＣＦ2)4ＣＦ(ＣＦ3)2、−Ｃ8Ｆ17等である。 In the above formula (1), the Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is preferably 1 to 6, particularly 4 to 6. Examples of Rf groups, -CF 3, -CF 2 CF 3 , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) 2 , -C (CF 3 ) 3 ,-(CF 2 ) 4 CF 3 ,-(CF 2 ) 2 CF (CF 3 ) 2 , -CF 2 C (CF 3 ) 3 , -CF (CF 3 ) CF 2 CF 2 CF 3 , — (CF 2 ) 5 CF 3 , — (CF 2 ) 3 CF (CF 3 ) 2 , — (CF 2 ) 4 CF (CF 3 ) 2 , —C 8 F 17 and the like.

Ｚは、炭素数１〜１０の脂肪族基、炭素数６〜１８の芳香族基または環状脂肪族基、
-CH2CH2N(R1)SO2−基（但し、R1は炭素数１〜４のアルキル基である。）、
-CH2CH(OZ1)CH2-(Ph-O)p-基（但し、Z1は水素原子またはアセチル基、Phはフェニレン基、ｐは０または１である。）、-(CH2)n-Ph-O-基（但し、Phはフェニレン基、ｎは０〜１０である。）、-(CH2)m−SO2−(CH2)n−基または -(CH2)m−S−(CH2)n−基（但し、mは１〜１０、nは０〜１０、である）であることが好ましい。脂肪族基は、アルキレン基（特に炭素数は１〜４、例えば１または２である。）であることが好ましい。芳香族基または環状脂肪族基は、置換または非置換であってよい。S 基または SO2基はRf基に直接に結合していてよい。 Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms),
-CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (where Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH 2 ) n -Ph-O-group (where, Ph is a phenylene radical, n is 0~10), -. (CH 2 ) m -SO 2 - (CH 2) n - group or - (CH 2) m It is preferably a —S— (CH 2 ) n — group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms). The aromatic group or cycloaliphatic group may be substituted or unsubstituted. The S group or SO 2 group may be directly bonded to the Rf group.

含フッ素単量体（a）の具体例としては、例えば以下のものを例示できるが、これらに限定されるものではない。   Specific examples of the fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.

CH2=C(−F)−C(=O)−O−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−Rf CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 2 −Rf

CH2=C(−F)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−F)−C(=O)−NH−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−NH−(CH2)2−Rf CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -NH- (CH 2 ) 2 -Rf

CH2=C(−CF3)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−NH−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−NH−(CH2)2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CN)−C(=O)−NH−(CH2)2−Rf CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CF 2 H) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CN) -C (= O) -NH- (CH 2 ) 2 -Rf

CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−NH−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−F)−C(=O)−NH−(CH2)3−Rf CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 3 -Rf

CH2=C(−Cl)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf

CH2=C(−CN)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
[上記式中、Ｒｆは、炭素数１〜２０のフルオロアルキル基である。] CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]

（ｂ）アルキルアクリレート単量体
アルキルアクリレート単量体（すなわち、非フッ素アルキルアクリレート単量体）は、アルキル基の炭素数が６〜１３であるアルキルアクリレートエステル（即ち、C6-13アルキル含有アルキルアクリレート）である。アルキルアクリレート単量体は、フッ素原子を含まない非フッ素単量体である。
アルキルアクリレート単量体において、α位が水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であってよい。α位は、水素原子またはメチル基であることが好ましく、水素原子であることが特に好ましい。 (B) Alkyl acrylate monomer An alkyl acrylate monomer (that is, a non-fluorine alkyl acrylate monomer) is an alkyl acrylate ester having an alkyl group having 6 to 13 carbon atoms (that is, a C 6-13 alkyl-containing alkyl). Acrylate). The alkyl acrylate monomer is a non-fluorine monomer containing no fluorine atom.
In the alkyl acrylate monomer, the α-position may be a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom). The α-position is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

アルキルアクリレート単量体は、式：
ＣＨ２＝ＣＡ１ＣＯＯＡ２
［式中、Ａ１は、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ａ２は、ＣｎＨ２ｎ＋１（ｎ＝６〜１３）によって表されるアルキル基である。］
で示されるアルキルアクリレートエステルであることが好ましい。
アルキル基の炭素数は、６〜１３、好ましくは８〜１２、例えば、１０〜１２である。アルキル基の炭素数を上記範囲にすることにより、処理剤における含フッ素重合体が低濃度であっても、優れた撥水性能、繰り返し洗濯による耐久性を与えることができる。
アルキルアクリレート単量体は、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレートであることが好ましい。ラウリル（メタ）アクリレートが特に好ましい。
本発明の含フッ素重合体は、Ａ２が炭素数１５以上のアルキル基（例えば、ステアリル基）である上記式（ＣＨ２＝ＣＡ１ＣＯＯＡ２）の単量体から誘導された繰り返し単位を有しないことが好ましい。 The alkyl acrylate monomer has the formula:
CH 2 = CA 1 COOA 2
[Wherein, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A 2 is an alkyl group represented by C n H 2n + 1 (n = 6 to 13). ]
It is preferable that it is the alkyl acrylate ester shown by these.
Carbon number of an alkyl group is 6-13, Preferably it is 8-12, for example, 10-12. By setting the carbon number of the alkyl group within the above range, excellent water repellency and durability by repeated washing can be imparted even when the concentration of the fluoropolymer in the treatment agent is low.
Alkyl acrylate monomers are hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl A (meth) acrylate is preferred. Lauryl (meth) acrylate is particularly preferred.
The fluoropolymer of the present invention has a repeating unit derived from a monomer of the above formula (CH 2 = CA 1 COOA 2 ), wherein A 2 is an alkyl group having 15 or more carbon atoms (eg, a stearyl group). Preferably not.

（ｃ）環状炭化水素基を有する非フッ素アクリレート単量体
環状炭化水素基を有する非フッ素アクリレート単量体（ｃ）は、フッ素原子を含まない単量体である。非フッ素アクリレート単量体（ｃ）は、架橋性官能基を有さない。非フッ素アクリレート単量体（ｃ）は、架橋性単量体（ｅ１）とは異なり、非架橋性である。 (C) Non-fluorine acrylate monomer having a cyclic hydrocarbon group The non-fluorine acrylate monomer (c) having a cyclic hydrocarbon group is a monomer containing no fluorine atom. The non-fluorine acrylate monomer (c) does not have a crosslinkable functional group. Unlike the crosslinkable monomer (e1), the nonfluorine acrylate monomer (c) is noncrosslinkable.

好ましい非フッ素アクリレート単量体（ｃ）は、式：
ＣＨ２＝ＣＡ−Ｃ(＝Ｏ)−Ｏ−Ｑ
［式中、Ａは、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ｑは、環状炭化水素基である。］
で示される化合物であってよい。 Preferred non-fluorinated acrylate monomers (c) have the formula:
CH 2 = CA-C (= O) -O-Q
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
Q is a cyclic hydrocarbon group. ]
It may be a compound shown by these.

環状炭化水素基の炭素数は、炭素数４〜３０、好ましくは４〜２０である。環状炭化水素基の例は、炭素数４〜３０、好ましくは４〜２０、特に５〜１２の環状脂肪族基、炭素数６〜３０、好ましくは６〜２０の芳香族炭化水素基、炭素数７〜３０、好ましくは７〜２０の芳香脂肪族炭化水素基である。
環状炭化水素基としては、飽和または不飽和である、単環基、多環基、橋かけ環基などが挙げられる。環状炭化水素基は、飽和であることが好ましい。
環状炭化水素基の炭素数は、１５以下、例えば１０以下であることが特に好ましい。環状炭化水素基の炭素数を上記範囲にすることにより、強撥水性を与えることができる。 The carbon number of the cyclic hydrocarbon group is 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, especially 5 to 12 cyclic aliphatic groups, 6 to 30 carbon atoms, preferably 6 to 20 aromatic hydrocarbon groups, and carbon atoms. 7-30, preferably 7-20 araliphatic hydrocarbon groups.
Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated.
The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. By setting the number of carbon atoms of the cyclic hydrocarbon group within the above range, strong water repellency can be provided.

環状炭化水素基の具体例は、シクロヘキシル基、ｔ−ブチルシクロヘキシル基、イソボルニル基、ジシクロペンタニル基、ジシクロペンテニル基である。アクリレート基は、アクリレート基またはメタアクリレート基であることが好ましいが、メタクリレート基が特に好ましい。環状炭化水素基を有する単量体の具体例としては、シクロヘキシル（メタ）アクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、トリシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、２−メチル−２−アダマンチル（メタ）アクリレート、２−エチル−２−アダマンチル（メタ）アクリレート等が挙げられる。   Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferable. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. , Dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-Adamantyl (meth) acrylate and the like.

（ｄ）ハロゲン化オレフィン単量体
ハロゲン化オレフィン単量体は、フッ素原子を含まない非フッ素単量体である。ハロゲン化オレフィン単量体は、１〜１０の塩素原子、臭素原子またはヨウ素原子で置換されている炭素数２〜２０、例えば２〜５のオレフィンであることが好ましい。ハロゲン化オレフィン単量体は、炭素数２〜２０の塩素化オレフィン、特に１〜５の塩素原子を有する炭素数２〜５のオレフィンであることが好ましい。ハロゲン化オレフィン単量体の好ましい具体例は、ハロゲン化ビニル、例えば塩化ビニル、臭化ビニル、ヨウ化ビニル、ハロゲン化ビニリデン、例えば塩化ビニリデン、臭化ビニリデン、ヨウ化ビニリデンである。撥水性または耐水性（特に、撥水性または耐水性の耐久性）が高くなるので、塩化ビニルが好ましい。 (D) Halogenated olefin monomer The halogenated olefin monomer is a non-fluorine monomer containing no fluorine atom. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms, for example 2 to 5 carbon atoms, substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride is preferable because of high water repellency or water resistance (particularly durability of water repellency or water resistance).

（ｅ）非フッ素単量体
非フッ素単量体（ｅ）は、アルキルアクリレート単量体（ｂ）、環状炭化水素基を有する非フッ素アクリレート単量体（ｃ）およびハロゲン化オレフィン単量体（ｄ）以外の非フッ素単量体である。非フッ素単量体（ｅ）は、非フッ素架橋性単量体（ｅ１）、または他の単量体（ｅ２）であってよい。 (E) Non-fluorine monomer The non-fluorine monomer (e) comprises an alkyl acrylate monomer (b), a non-fluorine acrylate monomer having a cyclic hydrocarbon group (c), and a halogenated olefin monomer ( It is a non-fluorine monomer other than d). The non-fluorine monomer (e) may be a non-fluorine crosslinkable monomer (e1) or another monomer (e2).

（ｅ１）非フッ素架橋性単量体
本発明の含フッ素重合体は、非フッ素架橋性単量体（ｅ１）から誘導された繰り返し単位を有していてよい。非フッ素架橋性単量体（ｅ１）は、フッ素原子を含まない単量体である。非フッ素架橋性単量体（ｅ１）は、少なくとも２つの反応性基および／または炭素−炭素二重結合を有し、フッ素を含有しない化合物であってよい。非フッ素架橋性単量体（ｅ１）は、少なくとも２つの炭素−炭素二重結合を有する化合物、あるいは少なくとも１つの炭素−炭素二重結合および少なくとも１つの反応性基を有する化合物であってよい。反応性基の例は、ヒドロキシル基、エポキシ基、クロロメチル基、ブロックイソシアネート基、アミノ基、カルボキシル基などである。非フッ素架橋性単量体（ｅ１）は、反応性基を有するモノ（メタ）アクリレート、ジ（メタ）アクリレートまたはモノ（メタ）アクリルアミドであってよい。あるいは、非フッ素架橋性単量体（ｅ１）は、ジ（メタ）アクリレートであってよい。 (E1) Non-fluorine crosslinkable monomer The fluorine-containing polymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (e1). The non-fluorine crosslinkable monomer (e1) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (e1) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine crosslinkable monomer (e1) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups and the like. The non-fluorine crosslinkable monomer (e1) may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (e1) may be di (meth) acrylate.

非フッ素架橋性単量体（ｅ１）としては、例えば、ジアセトン(メタ)アクリルアミド、(メタ)アクリルアミド、Ｎ−メチロール(メタ)アクリルアミド、ヒドロキシメチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、３−クロロ−２−ヒドロキシプロピル(メタ)アクリレート、2-アセトアセトキシエチル（メタ）アクリレート、ブタジエン、イソプレン、クロロプレン、グリシジル(メタ)アクリレート、１，６−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレートなどが例示されるが、これらに限定されるものでない。   Examples of the non-fluorine crosslinkable monomer (e1) include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include, but are not limited to, (meth) acrylate.

非フッ素単量体（ｅ２）は、単量体（ｅ１）以外の他の単量体である。他の単量体の具体例は、エチレン、酢酸ビニル、スチレン、α−メチルスチレン、ｐ−メチルスチレン、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルプロピル（メタ）アクリルアミド、メチロール化ジアセトン（メタ）アクリルアミド、ビニルアルキルエーテル、ハロゲン化アルキルビニルエーテル、ビニルアルキルケトン、アジリジニルエチル（メタ）アクリレート、アジリジニル（メタ）アクリレート、ポリオキシアルキレン（メタ）アクリレート、メチルポリオキシアルキレン（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、２−エチルヘキシルポリオキシアルキレン（メタ）アクリレート、ポリオキシアルキレンジ（メタ）アクリレート、ポリシロキサンを有する（メタ）アクリレート、トリアリルシアヌレート、アリルグリシジルエーテル、酢酸アリル、Ｎ−ビニルカルバゾール、マレイミド、Ｎ−メチルマレイミド、（２−ジメチルアミノ）エチル（メタ）アクリレート、側鎖にシリコーンを有する（メタ）アクリレート、ウレタン結合を有する（メタ）アクリレート、アルキレンジ（メタ）アクリレート、ポリオキシアルキレンジ（メタ）アクリレート等が挙げられる。   The non-fluorine monomer (e2) is another monomer other than the monomer (e1). Specific examples of other monomers include ethylene, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, N, N-dimethyl (meth) acrylamide, N, N-dimethylpropyl (meth) acrylamide, and methylolation. Diacetone (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, aziridinylethyl (meth) acrylate, aziridinyl (meth) acrylate, polyoxyalkylene (meth) acrylate, methyl polyoxyalkylene (meth) acrylate , Glycerol mono (meth) acrylate, 2-ethylhexyl polyoxyalkylene (meth) acrylate, polyoxyalkylene di (meth) acrylate, (meth) acrylate having polysiloxane, triallyl Anurate, allyl glycidyl ether, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (2-dimethylamino) ethyl (meth) acrylate, (meth) acrylate having silicone in the side chain, having urethane bond (meta ) Acrylate, alkylene di (meth) acrylate, polyoxyalkylene di (meth) acrylate and the like.

非フッ素単量体（ｅ）は、ヒドロキシル基を有する（メタ）アクリレート、および（メタ）アクリルアミド化合物の一方または両方を含んでなることが好ましい。ヒドロキシル基を有する（メタ）アクリレートにおいて、ヒドロキシル基の数は、１〜５、好ましくは２〜４、例えば２または３であってよい。-CH(OH)-CH2-OH基を有する（メタ）アクリレートが特に好ましい。（メタ）アクリルアミド化合物は、（メタ）アクリルアミド基を有する単量体である。（メタ）アクリルアミド化合物は、活性水素を有することが好ましく、ジアセトン(メタ)アクリルアミドであることが特に好ましい。ヒドロキシル基を有する（メタ）アクリレートおよび（メタ）アクリルアミド化合物は、撥水性を向上させる。非フッ素単量体（ｅ）として、ヒドロキシル基を有する（メタ）アクリレートおよび（メタ）アクリルアミド化合物の両方（例えば、重量比１：９〜１：９）を用いることが特に好ましい。 The non-fluorine monomer (e) preferably comprises one or both of a (meth) acrylate having a hydroxyl group and a (meth) acrylamide compound. In (meth) acrylates having hydroxyl groups, the number of hydroxyl groups may be 1-5, preferably 2-4, for example 2 or 3. A (meth) acrylate having a —CH (OH) —CH 2 —OH group is particularly preferred. A (meth) acrylamide compound is a monomer having a (meth) acrylamide group. The (meth) acrylamide compound preferably has active hydrogen, and particularly preferably diacetone (meth) acrylamide. (Meth) acrylate and (meth) acrylamide compounds having a hydroxyl group improve water repellency. As the non-fluorine monomer (e), it is particularly preferable to use both a (meth) acrylate having a hydroxyl group and a (meth) acrylamide compound (for example, a weight ratio of 1: 9 to 1: 9).

非フッ素アクリレート単量体（ｃ）および／または非フッ素架橋性単量体（ｅ１）を共重合させることにより、撥水撥油性や防汚性およびこれらの性能の耐クリーニング性、耐洗濯性、溶剤への溶解性、硬さ、感触などの種々の性質を必要に応じて改善することができる。   By copolymerizing the non-fluorinated acrylate monomer (c) and / or the non-fluorine crosslinkable monomer (e1), the water and oil repellency and antifouling properties and the cleaning resistance, washing resistance, Various properties such as solubility in a solvent, hardness, and feel can be improved as necessary.

本明細書において、単に「アクリレート」または「アクリルアミド」と呼ぶ場合には、α位が水素原子である化合物のみならず、α位が他の基（例えば、メチル基を含めた一価の有機基またはハロゲン原子）で置換されている化合物も含む。本明細書において、「（メタ）アクリレート」とは、アクリレートまたはメタクリレートを意味し、「（メタ）アクリルアミド」とは、アクリルアミドまたはメタクリルアミドを意味する。
単量体（ａ）、単量体（ｂ）、単量体（ｃ）、単量体（ｄ）および単量体（ｅ）（例えば、単量体（ｅ１）および（ｅ２）のそれぞれ）のそれぞれは、１種の単独であっても、または２種以上の組み合わせであってもよい。 In the present specification, when simply referred to as “acrylate” or “acrylamide”, not only a compound in which the α-position is a hydrogen atom, but also the α-position is another group (for example, a monovalent organic group including a methyl group). Or a compound substituted with a halogen atom). In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.
Monomer (a), Monomer (b), Monomer (c), Monomer (d) and Monomer (e) (for example, each of monomers (e1) and (e2)) Each of these may be a single species or a combination of two or more species.

含フッ素単量体（ａ）の量は、含フッ素重合体に対して２０重量％以上、好ましくは３０重量％〜９０重量％であってよい。
含フッ素単量体（ａ）１００重量部に対して、
アルキルアクリレート単量体（ｂ）の量が５〜３００重量部、例えば１０〜２００重量部、特に２０〜１００重量部、特別に３０〜８０重量部であり、
環状炭化水素基を有する非フッ素アクリレート単量体（ｃ）の量が０．１〜８００重量部、例えば１〜３００重量部、特に２〜２００重量部であり、特別に３〜１００重量部であり、
ハロゲン化オレンフィン（ｄ）の量が３００重量部、例えば５〜２００重量部、特に１０〜１５０重量部、特別に１５〜１００重量部であり、
非フッ素単量体（ｅ）の量が１０００重量部以下、例えば０．１〜４００重量部、特に０．５〜２５０重量部、特別に１〜５０重量部であってよい。
含フッ素重合体において、含フッ素単量体（ａ）１００重量部に対して、
非フッ素架橋性単量体（ｅ１）および（ｅ２）のそれぞれの量が８０重量部以下、例えば５０重量部以下、特に０．１〜３０重量部、特別に１〜２０重量部であってよい。
アルキルアクリレート単量体（ｂ）は、処理剤における含フッ素重合体が低濃度であっても、優れた撥水性能、繰り返し洗濯による耐久性を与えることができる。ハロゲン化オレフィン（ｄ）は、処理剤における含フッ素重合体がさらに低濃度であっても、撥水性能、耐洗濯性、耐ドライクリーニング性を与えることができる。環状炭化水素基を有する非フッ素アクリレート単量体（ｃ）は強撥水性を与えることができる。非フッ素架橋性単量体（ｅ１）は耐洗濯性を向上させることができる。 The amount of the fluorine-containing monomer (a) may be 20% by weight or more, preferably 30% by weight to 90% by weight with respect to the fluorine-containing polymer.
For 100 parts by weight of the fluorine-containing monomer (a),
The amount of the alkyl acrylate monomer (b) is 5 to 300 parts by weight, for example 10 to 200 parts by weight, in particular 20 to 100 parts by weight, especially 30 to 80 parts by weight,
The amount of the non-fluorinated acrylate monomer (c) having a cyclic hydrocarbon group is 0.1 to 800 parts by weight, for example 1 to 300 parts by weight, particularly 2 to 200 parts by weight, especially 3 to 100 parts by weight. Yes,
The amount of halogenated orenfin (d) is 300 parts by weight, for example 5 to 200 parts by weight, in particular 10 to 150 parts by weight, especially 15 to 100 parts by weight;
The amount of non-fluorine monomer (e) may be 1000 parts by weight or less, for example 0.1 to 400 parts by weight, in particular 0.5 to 250 parts by weight, especially 1 to 50 parts by weight.
In the fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing monomer (a),
The amount of each of the non-fluorine crosslinkable monomers (e1) and (e2) may be 80 parts by weight or less, such as 50 parts by weight or less, particularly 0.1 to 30 parts by weight, especially 1 to 20 parts by weight. .
The alkyl acrylate monomer (b) can provide excellent water repellency and durability by repeated washing even when the concentration of the fluoropolymer in the treatment agent is low. The halogenated olefin (d) can provide water repellency, washing resistance, and dry cleaning resistance even when the concentration of the fluoropolymer in the treatment agent is even lower. The non-fluorinated acrylate monomer (c) having a cyclic hydrocarbon group can give strong water repellency. The non-fluorine crosslinkable monomer (e1) can improve the washing resistance.

本発明における含フッ素重合体は通常の重合方法の何れでも製造でき、また重合反応の条件も任意に選択できる。このような重合方法として、溶液重合、懸濁重合、乳化重合が挙げられる。   The fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

溶液重合では、重合開始剤の存在下で、単量体を有機溶剤に溶解させ、窒素置換後、３０〜１２０℃の範囲で１〜１０時間、加熱撹拌する方法が採用される。重合開始剤としては、例えばアゾビスイソブチロニトリル、ベンゾイルパーオキシド、ジ−ｔ−ブチルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t−ブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネートなどが挙げられる。重合開始剤は単量体１００重量部に対して、０.０１〜２０重量部、例えば０.０１〜１０重量部の範囲で用いられる。   In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

有機溶媒は、単量体に不活性でこれらを溶解するものであり、例えば、エステル（例えば、炭素数２〜３０のエステル、具体的には、酢酸エチル、酢酸ブチル）、ケトン（例えば、炭素数２〜３０のケトン、具体的には、メチルエチルケトン、ジイソブチルケトン）、アルコール（例えば、炭素数１〜３０のアルコール、具体的には、イソプロピルアルコール）であってよい。有機溶媒の具体例としては、アセトン、クロロホルム、ＨＣＨＣ２２５、イソプロピルアルコール、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン、石油エーテル、テトラヒドロフラン、１,４−ジオキサン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、酢酸エチル、酢酸ブチル、１,１,２,２−テトラクロロエタン、１,１,１−トリクロロエタン、トリクロロエチレン、パークロロエチレン、テトラクロロジフルオロエタン、トリクロロトリフルオロエタンなどが挙げられる。有機溶媒は単量体の合計１００重量部に対して、１０〜２０００重量部、例えば、５０〜１０００重量部の範囲で用いられる。   The organic solvent is inactive to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having 2 to 30 (specifically, methyl ethyl ketone, diisobutyl ketone) or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

乳化重合では、重合開始剤および乳化剤の存在下で、単量体を水中に乳化させ、窒素置換後、５０〜８０℃の範囲で１〜１０時間、撹拌して共重合させる方法が採用される。重合開始剤は、過酸化ベンゾイル、過酸化ラウロイル、ｔ−ブチルパーベンゾエート、１−ヒドロキシシクロヘキシルヒドロ過酸化物、３−カルボキシプロピオニル過酸化物、過酸化アセチル、アゾビスイソブチルアミジン−二塩酸塩、アゾビスイソブチロニトリル、過酸化ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの水溶性のものやアゾビスイソブチロニトリル、ベンゾイルパーオキシド、ジ−ｔ−ブチルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t−ブチルパーオキシピバレート、ジイソプロピルパーオキシジカーボネートなどの油溶性のものが用いられる。重合開始剤は単量体１００重量部に対して、０.０１〜１０重量部の範囲で用いられる。   In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, is stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. . Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

放置安定性の優れた共重合体水分散液を得るためには、高圧ホモジナイザーや超音波ホモジナイザーのような強力な破砕エネルギーを付与できる乳化装置を用いて、単量体を水中に微粒子化し、油溶性重合開始剤を用いて重合することが望ましい。また、乳化剤としてはアニオン性、カチオン性あるいはノニオン性の各種乳化剤を用いることができ、単量体１００重量部に対して、０.５〜２０重量部の範囲で用いられる。アニオン性および／またはノニオン性および／またはカチオン性の乳化剤を使用してよい。ノニオン性の乳化剤を使用することが好ましい。乳化剤は、ノニオン性の乳化剤のみからなることが好ましい。単量体が完全に相溶しない場合は、これら単量体に充分に相溶させるような相溶化剤、例えば、水溶性有機溶剤や低分子量の単量体を添加することが好ましい。相溶化剤の添加により、乳化性および共重合性を向上させることが可能である。
水溶性有機溶剤としては、アセトン、メチルエチルケトン、酢酸エチル、プロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコール、トリプロピレングリコール、エタノールなどが挙げられ、水１００重量部に対して、１〜５０重量部、例えば１０〜４０重量部の範囲で用いてよい。また、低分子量の単量体としては、メチルメタクリレート、グリシジルメタクリレート、２,２,２−トリフルオロエチルメタクリレートなどが挙げられ、単量体の総量１００重量部に対して、１〜５０重量部、例えば１０〜４０重量部の範囲で用いてよい。 In order to obtain an aqueous copolymer dispersion with excellent storage stability, the monomer is finely divided into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to polymerize using a soluble polymerization initiator. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Anionic and / or nonionic and / or cationic emulsifiers may be used. It is preferable to use a nonionic emulsifier. The emulsifier is preferably composed of only a nonionic emulsifier. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.
Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

重合においては、連鎖移動剤を使用してもよい。連鎖移動剤の使用量に応じて、共重合体の分子量を変化させることができる。連鎖移動剤の例は、ラウリルメルカプタン、チオグリコール、チオグリセロールなどのメルカプタン基含有化合物（特に、（例えば炭素数１〜３０の）アルキルメルカプタン）、次亜リン酸ナトリウム、亜硫酸水素ナトリウムなどの無機塩などである。連鎖移動剤の使用量は、単量体の総量１００重量部に対して、０．０１〜１０重量部、例えば０．１〜５重量部の範囲で用いてよい。   In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the copolymer can be varied. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc. You may use the usage-amount of a chain transfer agent in 0.01-10 weight part with respect to 100 weight part of total amounts of a monomer, for example, 0.1-5 weight part.

得られた含フッ素重合体は、必要により水や有機溶剤等に希釈または分散された後、乳濁液、有機溶剤溶液、エアゾールなどの任意の形態に調製でき、処理剤とすることが可能である。含フッ素重合体は、処理剤の有効成分（活性成分）として機能する。処理剤は、含フッ素重合体および媒体（特に、液状媒体）（例えば、有機溶媒および／または水）を含んでなる。処理剤において、含フッ素重合体の濃度は、例えば、０．０１〜５０重量％であってよい。
本発明の処理剤は、含フッ素重合体および水性媒体を含んでなることが好ましい。本明細書において、「水性媒体」とは、水のみからなる媒体、および水に加えて有機溶剤（水溶性有機溶剤）（有機溶剤の量は、水１００重量部に対して、８０重量部以下、例えば０．１〜５０重量部、特に５〜３０重量部である。）をも含有する媒体を意味する。含フッ素重合体は、乳化重合によって、含フッ素重合体の分散液を製造されたものであることが好ましい。処理剤は、含フッ素重合体の粒子が水性媒体に分散する水性分散液であることが好ましい。 The resulting fluoropolymer can be prepared in any form such as an emulsion, organic solvent solution, aerosol, etc. after being diluted or dispersed in water or an organic solvent, if necessary, and can be used as a treatment agent. is there. The fluorine-containing polymer functions as an active ingredient (active ingredient) of the treating agent. The treatment agent comprises a fluoropolymer and a medium (particularly a liquid medium) (for example, an organic solvent and / or water). In the treatment agent, the concentration of the fluoropolymer may be, for example, 0.01 to 50% by weight.
The treatment agent of the present invention preferably comprises a fluoropolymer and an aqueous medium. In the present specification, the term “aqueous medium” refers to a medium composed only of water and an organic solvent (water-soluble organic solvent) in addition to water (the amount of the organic solvent is 80 parts by weight or less with respect to 100 parts by weight of water. For example 0.1 to 50 parts by weight, in particular 5 to 30 parts by weight). The fluorine-containing polymer is preferably one obtained by producing a dispersion of a fluorine-containing polymer by emulsion polymerization. The treating agent is preferably an aqueous dispersion in which the fluoropolymer particles are dispersed in an aqueous medium.

本発明の含フッ素重合体は、被処理物品の種類や前記調製形態（乳濁液、有機溶剤溶液、エアゾールなど）などに応じて、任意の方法で処理剤として被処理物品に適応され得る。例えば、水性乳濁液や有機溶剤溶液である場合には、浸漬塗布、スプレー塗布等のような被覆加工の既知の方法により、被処理物の表面に付着させ乾燥する方法が採用され得る。この際、必要ならばキュアリング等の熱処理を行っても良い。
また、必要ならば、他のブレンダーを併用することも可能である。例えば、撥水撥油剤、防シワ剤、防縮剤、難燃剤、架橋剤、帯電防止剤、柔軟剤、ポリエチレングリコールやポリビニルアルコール等の水溶性高分子、ワックスエマルション、抗菌剤、顔料、塗料などである。これらのブレンダーは被処理物、処理時に処理浴に添加して使用しても良いし、あらかじめ、可能なら、本発明の含フッ素重合体と混合して使用しても良い。 The fluoropolymer of the present invention can be applied to the article to be treated as a treating agent by any method depending on the kind of article to be treated and the preparation form (emulsion, organic solvent solution, aerosol, etc.). For example, in the case of an aqueous emulsion or an organic solvent solution, a method of adhering to a surface of an object to be processed and drying by a known method of coating processing such as dip coating or spray coating can be employed. At this time, if necessary, heat treatment such as curing may be performed.
If necessary, other blenders can be used together. For example, water / oil repellent, wrinkle preventive, anti-shrink agent, flame retardant, crosslinking agent, antistatic agent, softener, water-soluble polymer such as polyethylene glycol and polyvinyl alcohol, wax emulsion, antibacterial agent, pigment, paint, etc. is there. These blenders may be used by being added to the object to be treated and the treatment bath at the time of treatment, or in advance, if possible, mixed with the fluoropolymer of the present invention.

含フッ素重合体は、基材布の上に重合体の膜を形成するために知られている方法のいずれかによって基材布に適用することができる。一般に、含フッ素重合体および液状媒体を含む液を布基材上に適用した後、液状媒体を乾燥などにより除去することによって、含フッ素重合体の膜を基材上に形成することができる。含フッ素重合体および液状媒体を含む液において、含フッ素重合体の濃度は、例えば、０．０１〜２０重量％、特に０．０５〜１０重量％であってよい。基材布を溶液に浸してよく、あるいは、基材布に液を付着または噴霧してよい。液を適用した基材布は、例えば撥液性を発現させるために、乾燥され、好ましくは、例えば、１００℃〜２００℃で加熱される。   The fluoropolymer can be applied to the base fabric by any of the known methods for forming a polymer film on the base fabric. In general, after a liquid containing a fluoropolymer and a liquid medium is applied to a cloth substrate, the liquid medium is removed by drying or the like, whereby a fluoropolymer film can be formed on the substrate. In the liquid containing the fluoropolymer and the liquid medium, the concentration of the fluoropolymer may be, for example, 0.01 to 20% by weight, particularly 0.05 to 10% by weight. The substrate cloth may be immersed in the solution, or the liquid may be attached to or sprayed on the substrate cloth. The base fabric to which the liquid is applied is dried, for example, to exhibit liquid repellency, and is preferably heated at, for example, 100 ° C. to 200 ° C.

被処理物品としては、特に限定されないが繊維製品の他、石材、フィルター（例えば、静電フィルター）、防塵マスク、ガラス、紙、木、皮革、毛皮、石綿、レンガ、セメント、金属および酸化物、窯業製品、プラスチック、塗面、およびプラスターなどを挙げることができる。特に繊維製品に対して有用である。繊維製品としては種々の例を挙げることができる。例えば、綿、麻、羊毛、絹などの動植物性天然繊維、ポリアミド、ポリエステル、ポリビニルアルコール、ポリアクリロニトリル、ポリ塩化ビニル、ポリプロピレンなどの合成繊維、レーヨン、アセテートなどの半合成繊維、ガラス繊維、炭素繊維、アスベスト繊維などの無機繊維、あるいはこれらの混合繊維が挙げられる。繊維製品は、繊維、糸、布等の形態のいずれであってもよい。   The article to be treated is not particularly limited, but besides textiles, stones, filters (for example, electrostatic filters), dust masks, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, Mention may be made of ceramic products, plastics, painted surfaces and plasters. It is particularly useful for textile products. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof. The fiber product may be in the form of fiber, yarn, cloth or the like.

本発明においては、被処理物品を処理剤で処理する。「処理」とは、処理剤を、浸漬、噴霧、塗布などにより被処理物に適用することを意味する。処理により、処理剤の有効成分である含フッ素共重合体が被処理物の内部に浸透するおよび／または被処理物の表面に付着する。   In the present invention, the article to be treated is treated with a treating agent. “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the fluorine-containing copolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

次に、実施例、比較例及び試験例を挙げて本発明を具体的に説明する。ただし、これらの説明が本発明を限定するものでない。
以下において、部または％は、特記しない限り、重量部または重量％を表す。
特性は、次のようにして測定した。 Next, an Example, a comparative example, and a test example are given and this invention is demonstrated concretely. However, these explanations do not limit the present invention.
In the following, parts or% represents parts by weight or% by weight unless otherwise specified.
The characteristics were measured as follows.

低濃度撥水性
重合体の水性分散液を固形分濃度が０．１５、０．２３、０．３重量％になるよう水で希釈して処理液を調整した。ナイロン布（４０デニール、タフタ）を処理液に浸漬し、マングルで４ｋｇ／ｃｍ２、４ｍ／分で絞って、１７０℃で１分間熱処理した後に、処理布の撥水性を評価した。
撥水性は、ＪＩＳ−Ｌ−１０９２のスプレー法による撥水性NO.（下記表１参照）をもって表す。なお、下記の撥水性NO.に＋を付けて表した評価結果はそれぞれの評価がその数字よりもわずかに良好なものを、−はわずかに低いことを示す。 A treatment liquid was prepared by diluting an aqueous dispersion of a low-concentration water-repellent polymer with water so that the solid concentration was 0.15, 0.23, or 0.3% by weight. Nylon cloth (40 denier, taffeta) was dipped in the treatment liquid, squeezed with mangle at 4 kg / cm 2 , 4 m / min, and heat treated at 170 ° C. for 1 minute, and then the water repellency of the treated cloth was evaluated.
The water repellency is represented by a water repellency NO. (See Table 1 below) by the spray method of JIS-L-1092. In addition, the evaluation result which attached | subjected + to the following water-repellent NO. Shows that each evaluation is slightly better than the number, and-is slightly low.

Figure 2015108131
Figure 2015108131

耐久撥水性
重合体の水性分散液を固形分濃度が１．０重量％になるよう水で希釈し、さらにブロックドイソシアネート（第一工業製薬製、商品名「エラストロンＢＮ−６９」）を０．２５重量％となるように添加して処理液を調整した。試験布を処理液に浸漬し、マングルで４ｋｇ／ｃｍ２、４ｍ／分で絞って、ナイロン布（７０デニール、タフタ）は１７０℃で１分間、ポリエステル（７０デニール、タフタ）は１２０℃で２分間、ポリエステル（２０デニール、リップ）は１００℃で２分間熱処理した後に、処理布の撥水性を評価した。
撥水性は、洗濯前（ＨＬ０）とＡＡＴＣＣ ８８Ｂ（１）（III）に準じて１０回または２０回繰り返し洗濯を行なった後（ＨＬ１０またはＨＬ２０）に評価した。撥水性は、低濃度撥水性と同じくＪＩＳ−Ｌ−１０９２のスプレー法による撥水性NO.（上記表１参照）をもって表す。 The aqueous dispersion of the durable water-repellent polymer was diluted with water so that the solid content concentration was 1.0% by weight, and blocked isocyanate (trade name “Elastolon BN-69” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The treatment solution was adjusted by adding 25% by weight. Immerse the test cloth in the treatment solution, squeeze it with a mangle at 4 kg / cm 2 and 4 m / min, nylon cloth (70 denier, taffeta) for 1 minute at 170 ° C., polyester (70 denier, taffeta) at 120 ° C. The polyester (20 denier, lip) was heat treated for 2 minutes at 100 ° C. for 2 minutes, and then the water repellency of the treated fabric was evaluated.
Water repellency was evaluated before washing (HL0) and after washing was repeated 10 or 20 times (HL10 or HL20) according to AATCC 88B (1) (III). The water repellency is expressed by the water repellency NO. (See Table 1 above) by the spray method of JIS-L-1092 as well as the low concentration water repellency.

ポリマーのタック性
重合体の水性分散液10gをメタノール20gに分散したものを60分間10000rpmで遠心分離器にかけて重合体と乳化剤を分離し、測定用サンプルポリマーを得た。このポリマーのタック性はタッキング試験機 TAC-2((株)RHESCA社製)で測定した。サンプルポリマー 0.1g，測定温度40℃，荷重500gfでタック性を測定した。 A sample polymer for measurement was obtained by separating 10 g of an aqueous dispersion of a tacky polymer of polymer in 20 g of methanol and separating the polymer and the emulsifier by centrifuging at 10,000 rpm for 60 minutes. The tackiness of this polymer was measured with a tacking tester TAC-2 (manufactured by RHESCA). The tackiness was measured at 0.1 g of sample polymer, a measurement temperature of 40 ° C, and a load of 500 gf.

実施例１
１Ｌオートクレーブに単量体Ａ：Ｃ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（Ｃｌ）＝ＣＨ２（Ｃ６ＳＦＣＬＡ） １１０ｇ、単量体Ｂ：ラウリルメタクリレート（ＬＭＡ）４８ｇ、単量体Ｄ：シクロヘキシルメタクリレート（ＣＨＭＡ）４２ｇ、純水 ４４６ｇ、トリプロピレングリコール ７６ｇ、ポリオキシエチレンラウリルエーテル １０．２ｇ、ポリオキシエチレンオレイルエーテル ２．４７ｇ、ポリオキシエチレンイソトリデシルエーテル７．６ｇを入れ、６０℃で加温後、高圧ホモジナイザーで乳化分散させた。乳化後、ラウリルメルカプタン２．５ｇ、単量体Ｃ：塩化ビニル（ＶＣｌ） ６２ｇを圧入充填した。さらに２，２−アゾビス（２−アミジノプロパン）２塩酸塩 １．６ｇを添加し、７０℃で３時間反応させ、重合体の水性分散液を得た。その固形分濃度が３０重量％となるように純水で濃度調整した水性分散液の撥水性（撥水撥油性能）およびタック性を評価した。結果を表２に示す。 Example 1
Monomer A: C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2 (C6SFCLA) 110 g, monomer B: lauryl methacrylate (LMA) 48 g, monomer D: cyclohexyl methacrylate (CHMA) 42 g, pure water 446 g, tripropylene glycol 76 g, polyoxyethylene lauryl ether 10.2 g, polyoxyethylene oleyl ether 2.47 g, polyoxyethylene isotridecyl ether 7.6 g were added, heated at 60 ° C. and then high pressure The mixture was emulsified and dispersed with a homogenizer. After emulsification, 2.5 g of lauryl mercaptan and 62 g of monomer C: vinyl chloride (VCl) were injected and filled. Further, 1.6 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 70 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. The water repellency (water / oil repellency) and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% by weight were evaluated. The results are shown in Table 2.

実施例２
単量体Ｂとしてラウリルアクリレート（ＬＡ）を用い、単量体Ｃ：塩化ビニル（ＶＣｌ）を省略し、単量体Ｆ：グリセロールモノメタクリレート（ＧＬＭ）を加えた以外は実施例１と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 2
Example 1 except that lauryl acrylate (LA) is used as monomer B, monomer C: vinyl chloride (VCl) is omitted, and monomer F: glycerol monomethacrylate (GLM) is added. An aqueous dispersion of polymer was obtained (see Table 2 for charged amounts of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例３
単量体Ｂとしてオクチルアクリレート（ＯＡ）を用い、単量体Ｅ：ダイアセトンアクリルアミド（ＤＡＡＭ）および単量体Ｆ：グリセロールモノメタクリレート（ＧＬＭ）を加えた以外は実施例１と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 3
Polymer as in Example 1 except that octyl acrylate (OA) was used as monomer B and monomer E: diacetone acrylamide (DAAM) and monomer F: glycerol monomethacrylate (GLM) were added. (Refer to Table 2 for the charged amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例４
単量体Ｂとしてイソオクチルアクリレート（ｉｓｏ−ＯＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 4
Except that isooctyl acrylate (iso-OA) was used as the monomer B, an aqueous polymer dispersion was obtained in the same manner as in Example 3 (see Table 2 for charged amounts of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例５
単量体Ｂとしてイソデシルアクリレート（ｉｓｏ−ＤＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 5
Except that isodecyl acrylate (iso-DA) was used as the monomer B, an aqueous dispersion of the polymer was obtained in the same manner as in Example 3 (see Table 2 for the charged amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例６
単量体Ｂとしてラウリルアクリレート（ＬＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 6
An aqueous polymer dispersion was obtained in the same manner as in Example 3 except that lauryl acrylate (LA) was used as the monomer B (see Table 2 for charged amounts of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例７
単量体Ｄ：ベンジルメタクリレート（ＢｚＭＡ）を加え、単量体Ｅ：ダイアセトンアクリルアミド（ＤＡＡＭ）を省略した以外は、実施例６と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 7
Monomer D: An aqueous polymer dispersion was obtained in the same manner as in Example 6 except that benzyl methacrylate (BzMA) was added and monomer E: diacetone acrylamide (DAAM) was omitted. (See Table 2 for the charge amount). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例８
単量体Ｄとしてイソボルニルメタクリレート（ＩＢＭＡ）を用いた以外は、実施例６と同様にして重合体の水性分散液を得た（各成分の仕込量は表２参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 8
An aqueous dispersion of polymer was obtained in the same manner as in Example 6 except that isobornyl methacrylate (IBMA) was used as the monomer D (see Table 2 for the charged amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 2.

実施例９
１Ｌオートクレーブに単量体Ａ：Ｃ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（Ｃｌ）＝ＣＨ２（Ｃ６ＳＦＣＬＡ） １５０ｇ、単量体Ｂ：ラウリルアクリレート（ＬＡ）７０ｇ、単量体Ｄ：イソボロニルメタクリレート（ＩＢＭＡ）３０ｇ、純水 ４４６ｇ、トリプロピレングリコール ７６ｇ、ポリオキシエチレンラウリルエーテル １０．２ｇ、ポリオキシエチレンオレイルエーテル ２．４７ｇ、ポリオキシエチレンイソトリデシルエーテル７．６ｇを入れ、６０℃で加温後、高圧ホモジナイザーで乳化分散させた。乳化後、ラウリルメルカプタン２．５ｇを添加した。さらに２，２−アゾビス（２−アミジノプロパン）２塩酸塩 １．６ｇを添加し、７０℃で３時間反応させ、重合体の水性分散液を得た。その固形分濃度が３０重量％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表２に示す。 Example 9
In a 1 L autoclave, monomer A: C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2 (C6SFCLA) 150 g, monomer B: lauryl acrylate (LA) 70 g, monomer D: isoboronyl methacrylate ( (IBMA) 30 g, pure water 446 g, tripropylene glycol 76 g, polyoxyethylene lauryl ether 10.2 g, polyoxyethylene oleyl ether 2.47 g, polyoxyethylene isotridecyl ether 7.6 g, and heated at 60 ° C. And emulsified and dispersed with a high-pressure homogenizer. After emulsification, 2.5 g of lauryl mercaptan was added. Further, 1.6 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 70 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% by weight were evaluated. The results are shown in Table 2.

比較例１
１Ｌオートクレーブに単量体Ａ：Ｃ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（Ｃｌ）＝ＣＨ２（Ｃ６ＳＦＣＬＡ） １５０ｇ、単量体Ｂ：ステアリルアクリレート（ＳｔＡ）５３ｇ、純水 ４４６ｇ、トリプロピレングリコール ７６ｇ、ポリオキシエチレンラウリルエーテル １０．２ｇ、ポリオキシエチレンオレイルエーテル ２．４７ｇ、ポリオキシエチレンイソトリデシルエーテル７．６ｇを入れ、６０℃で加温後、高圧ホモジナイザーで乳化分散させた。乳化後、ラウリルメルカプタン２．５ｇ、単量体Ｃ：塩化ビニル（ＶＣｌ） ６２ｇを圧入充填した。さらに２，２−アゾビス（２−アミジノプロパン）２塩酸塩 １．６ｇを添加し、７０℃で３時間反応させ、重合体の水性分散液を得た。その固形分濃度が３０重量％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 1
Monomer A: C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2 (C6SFCLA) 150 g, monomer B: stearyl acrylate (StA) 53 g, pure water 446 g, tripropylene glycol 76 g, 1 L autoclave 10.2 g of oxyethylene lauryl ether, 2.47 g of polyoxyethylene oleyl ether and 7.6 g of polyoxyethylene isotridecyl ether were added, heated at 60 ° C., and then emulsified and dispersed with a high-pressure homogenizer. After emulsification, 2.5 g of lauryl mercaptan and 62 g of monomer C: vinyl chloride (VCl) were injected and filled. Further, 1.6 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 70 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% by weight were evaluated. The results are shown in Table 3.

比較例２
単量体Ｃ：塩化ビニル（ＶＣｌ）省略した以外は、比較例１と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 2
Monomer C: An aqueous dispersion of polymer was obtained in the same manner as in Comparative Example 1 except that vinyl chloride (VCl) was omitted (see Table 3 for charged amounts of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

比較例３
単量体ＡとしてＣ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２（Ｃ６ＳＦＭＡ）を用い、単量体Ｂとしてラウリルアクリレート（ＬＡ）を用いた以外は、比較例２と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 3
The same as Comparative Example 2 except that C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) ═CH 2 (C6SFMA) was used as the monomer A, and lauryl acrylate (LA) was used as the monomer B. An aqueous dispersion of the polymer was obtained (see Table 3 for the charge amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

比較例４
単量体Ｂとしてブチルアクリレート（ＢＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 4
An aqueous polymer dispersion was obtained in the same manner as in Example 3 except that butyl acrylate (BA) was used as the monomer B (see Table 3 for charged amounts of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

比較例５
単量体Ｂとしてセチルアクリレート（ＣＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 5
An aqueous polymer dispersion was obtained in the same manner as in Example 3 except that cetyl acrylate (CA) was used as the monomer B (see Table 3 for charged amounts of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

比較例６
単量体Ｂとしてステアリルアクリレート（ＳｔＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 6
Except that stearyl acrylate (StA) was used as the monomer B, an aqueous dispersion of the polymer was obtained in the same manner as in Example 3 (see Table 3 for the charge amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

比較例７
単量体Ｂとしてベヘニルアクリレート（ＢｅＡ）を用いた以外は、実施例３と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 7
An aqueous dispersion of a polymer was obtained in the same manner as in Example 3 except that behenyl acrylate (BeA) was used as the monomer B (see Table 3 for the charged amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

比較例８
単量体ＡとしてＣ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２（Ｃ６ＳＦＭＡ）、単量体Ｂとしてステアリルアクリレート（ＳｔＡ）、単量体Ｄとしてシクロヘキシルメタクリレート（ＣＨＭＡ）を用いた以外は、実施例７と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。
比較例９
単量体Ｂとしてステアリルアクリレート（ＳｔＡ）を用いた以外は、実施例９と同様にして重合体の水性分散液を得た（各成分の仕込量は表３参照）。その固形分濃度が３０％となるように純水で濃度調整した水性分散液の撥水性およびタック性を評価した。結果を表３に示す。 Comparative Example 8
Except for using C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) ═CH 2 (C 6 SFMA) as the monomer A, stearyl acrylate (StA) as the monomer B, and cyclohexyl methacrylate (CHMA) as the monomer D Obtained an aqueous dispersion of a polymer in the same manner as in Example 7 (see Table 3 for the charge amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.
Comparative Example 9
Except that stearyl acrylate (StA) was used as the monomer B, an aqueous dispersion of the polymer was obtained in the same manner as in Example 9 (see Table 3 for the charged amount of each component). The water repellency and tackiness of an aqueous dispersion whose concentration was adjusted with pure water so that the solid content concentration was 30% were evaluated. The results are shown in Table 3.

表中の略号の意味は、次のとおりである。
＜単量体Ａ＞
Ｃ６ＳＦＣＬＡ：Ｃ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（Ｃｌ）＝ＣＨ２
Ｃ６ＳＦＭＡ：Ｃ６Ｆ１３ＣＨ２ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２ The meanings of the abbreviations in the table are as follows.
<Monomer A>
C6SFCLA: C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2
C6SFMA: C 6 F 13 CH 2 CH 2 OCOC (CH 3) = CH 2

＜単量体Ｂ＞
ＬＡ：ラウリルアクリレート
ＬＭＡ：ラウリルメタクリレート
ＯＡ：オクチルアクリレート
ｉｓｏ−ＯＡ：イソオクチルアクリレート
ｉｓｏ−ＤＡ：イソデシルアクリレート
ＳｔＡ：ステアリルアクリレート
ＢＡ：ブチルアクリレート
ＣＡ：セチルアクリレート
ＢｅＡ：ベヘニルアクリレート <Monomer B>
LA: lauryl acrylate LMA: lauryl methacrylate OA: octyl acrylate iso-OA: isooctyl acrylate iso-DA: isodecyl acrylate StA: stearyl acrylate BA: butyl acrylate CA: cetyl acrylate BeA: behenyl acrylate

＜単量体Ｃ＞
ＶＣｌ：塩化ビニル <Monomer C>
VCl: Vinyl chloride

＜単量体Ｄ＞
ＣＨＭＡ：シクロヘキシルメタクリレート
ＢｚＭＡ：ベンジルメタクリレート
ＩＢＭＡ：イソボルニルメタクリレート <Monomer D>
CHMA: cyclohexyl methacrylate BzMA: benzyl methacrylate IBMA: isobornyl methacrylate

＜単量体Ｅ＞
ＤＡＡＭ：ダイアセトンアクリルアミド
＜単量体Ｆ＞
ＧＬＭ：グリセロールモノメタクリレート
＜布＞
Ｎｙ：ナイロン布（７０デニール、タフタ）
ＰＥＴ ７０ｄ：ポリエステル（７０デニール、タフタ）
ＰＥＴ ２０ｄ：ポリエステル（２０デニール、リップ） <Monomer E>
DAAM: Diacetone acrylamide <Monomer F>
GLM: Glycerol monomethacrylate <cloth>
Ny: Nylon cloth (70 denier, taffeta)
PET 70d: Polyester (70 denier, taffeta)
PET 20d: Polyester (20 denier, lip)

Figure 2015108131
Figure 2015108131

Figure 2015108131
Figure 2015108131

本発明の含フッ素重合体は、処理剤、特に表面処理剤、例えば、撥水撥油剤、防汚剤および汚れ脱離剤の有効成分として使用できる。   The fluoropolymer of the present invention can be used as an active ingredient of a treating agent, particularly a surface treating agent, for example, a water / oil repellent, an antifouling agent and a soil release agent.

本発明の態様は、次のとおりである。
＜１＞
（ａ）α位が一価の有機基またはハロゲン原子で置換されているアクリレートエステル単量体である、フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位、および
（ｂ）アルキル基の炭素数が６〜１３であるアルキルアクリレートである非フッ素単量体から誘導された繰り返し単位
を有してなる含フッ素重合体。
＜２＞
含フッ素単量体（ａ）が、式：
CH2=C(-X)-C(=O)-Y-Z-Rf
［式中、Ｘは、一価の有機基またはハロゲン原子であり、
Y は、-O- または -NH-であり、
Ｚは、直接結合または二価の有機基であり、
Ｒｆは、炭素数１〜２０のフルオロアルキル基である。］
で示される化合物である＜１＞に記載の含フッ素重合体。 Aspects of the present invention are as follows.
<1>
(A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group, which is an acrylate ester monomer substituted at the α-position with a monovalent organic group or a halogen atom, and (b) an alkyl group A fluorine-containing polymer having a repeating unit derived from a non-fluorine monomer which is an alkyl acrylate having 6 to 13 carbon atoms.
<2>
The fluorine-containing monomer (a) has the formula:
CH 2 = C (-X) -C (= O) -YZ-Rf
[Wherein X is a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a C1-C20 fluoroalkyl group. ]
The fluorine-containing polymer according to <1>, which is a compound represented by the formula:

＜３＞
含フッ素単量体（ａ）が、式：
CH2=C(−X)−C(=O)−Y−Z−Rf （Ｉ）
［式中、Ｘは、炭素数２〜２１の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ1Ｘ2基（但し、Ｘ1およびＸ2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基であり；
Ｙは、−Ｏ−または−ＮＨ−であり；
Ｚは、炭素数１〜１０の脂肪族基、炭素数６〜１８の芳香族基または環状脂肪族基、
-CH2CH2N(R1)SO2−基（但し、R1は炭素数１〜４のアルキル基である。）または
-CH2CH(OZ1) CH2−基（但し、Z1は水素原子またはアセチル基である。）または
-(CH2)m−SO2−(CH2)n−基または -(CH2)m−S−(CH2)n−基（但し、mは１〜１０、nは０〜１０、である）、
Ｒｆは、炭素数１〜２０の直鎖状または分岐状のフルオロアルキル基である。]
で示される化合物である＜１＞または＜２＞に記載の含フッ素重合体。 <3>
The fluorine-containing monomer (a) has the formula:
CH 2 = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where X 1 and X 2 are A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, substituted or non-substituted A substituted phenyl group;
Y is —O— or —NH—;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or
-CH 2 CH (OZ 1 ) CH 2 -group (where Z 1 is a hydrogen atom or an acetyl group) or
— (CH 2 ) m —SO 2 — (CH 2 ) n — group or — (CH 2 ) m —S— (CH 2 ) n — group (where m is 1 to 10, n is 0 to 10, is there),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
The fluorine-containing polymer according to <1> or <2>, which is a compound represented by the formula:

＜４＞
含フッ素単量体（ａ）が、α位が塩素原子で置換されているアルキルアクリレートである＜１＞〜＜３＞のいずれかに記載の含フッ素重合体。
＜５＞
非フッ素単量体（ｂ）が、式：
ＣＨ２＝ＣＡ１ＣＯＯＡ２
［式中、Ａ１は、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ａ２は、ＣｎＨ２ｎ＋１（ｎ＝６〜１３）によって表されるアルキル基である。］
で示されるアルキルアクリレートである＜１＞〜＜４＞のいずれかに記載の含フッ素重合体。
＜６＞
非フッ素単量体（ｂ）においてアルキル基の炭素数が８〜１３である＜１＞〜＜５＞のいずれかに記載の含フッ素重合体。 <4>
The fluorine-containing polymer according to any one of <1> to <3>, wherein the fluorine-containing monomer (a) is an alkyl acrylate substituted at the α-position with a chlorine atom.
<5>
The non-fluorine monomer (b) has the formula:
CH 2 = CA 1 COOA 2
[Wherein, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A 2 is an alkyl group represented by C n H 2n + 1 (n = 6 to 13). ]
The fluorine-containing polymer according to any one of <1> to <4>, which is an alkyl acrylate represented by
<6>
The fluorine-containing polymer according to any one of <1> to <5>, wherein the alkyl group in the non-fluorine monomer (b) has 8 to 13 carbon atoms.

＜７＞
含フッ素重合体が、さらに、
（ｃ）ハロゲン化オレフィン単量体から誘導された繰り返し単位、および
（ｄ）単量体（ｂ）および（ｃ）以外の非フッ素単量体から誘導された繰り返し単位
からなる群から選択された少なくとも１種の繰り返し単位を有する＜１＞〜＜６＞のいずれかに記載の含フッ素重合体。
＜８＞
ハロゲン化オレフィン単量体（ｃ）が、１〜１０の塩素原子、臭素原子またはヨウ素原子で置換されている炭素数２〜２０のオレフィンである＜７＞に記載の含フッ素重合体。
＜９＞
非フッ素単量体（ｄ）が、環状炭化水素基を有する非フッ素（メタ）アクリレート単量体（ｄ１）および非フッ素架橋性単量体（ｄ２）からなる群から選択された少なくとも１種である＜７＞または＜８＞に記載の含フッ素重合体。 <7>
The fluorine-containing polymer is further
(C) selected from the group consisting of repeating units derived from halogenated olefin monomers, and (d) repeating units derived from non-fluorine monomers other than monomers (b) and (c) The fluorine-containing polymer according to any one of <1> to <6>, which has at least one repeating unit.
<8>
The fluorine-containing polymer according to <7>, wherein the halogenated olefin monomer (c) is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms.
<9>
The non-fluorine monomer (d) is at least one selected from the group consisting of a non-fluorine (meth) acrylate monomer (d1) having a cyclic hydrocarbon group and a non-fluorine crosslinkable monomer (d2). The fluorine-containing polymer according to <7> or <8>.

＜１０＞
環状炭化水素基を有する非フッ素（メタ）アクリレート単量体（ｄ１）が、式：
ＣＨ２＝ＣＡ−Ｃ(＝Ｏ)−Ｏ−Ｑ
［式中、Ａは、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ｑは、環状炭化水素基である。］
で示される化合物である＜９＞に記載の含フッ素重合体。
＜１１＞
非フッ素架橋性単量体（ｄ２）が、少なくとも２つの反応性基および／または炭素−炭素二重結合を有する単量体であり、反応性基がヒドロキシル基、エポキシ基、クロロメチル基、ブロックドイソシアネート、アセトアセトキシ基、アミノ基またはカルボキシル基である＜９＞に記載の含フッ素重合体。 <10>
The non-fluorine (meth) acrylate monomer (d1) having a cyclic hydrocarbon group has the formula:
CH 2 = CA-C (= O) -O-Q
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
Q is a cyclic hydrocarbon group. ]
The fluorine-containing polymer according to <9>, which is a compound represented by the formula:
<11>
The non-fluorine crosslinkable monomer (d2) is a monomer having at least two reactive groups and / or carbon-carbon double bonds, and the reactive group is a hydroxyl group, an epoxy group, a chloromethyl group, a block <9> The fluorine-containing polymer according to <9>, which is deisocyanate, acetoacetoxy group, amino group or carboxyl group.

＜１２＞
含フッ素単量体（ａ）１００重量部に対して、アクリレートエステル単量体（ｂ）の量が５〜３００重量部である＜１＞〜＜１１＞のいずれかに記載の含フッ素重合体。
＜１３＞
＜１＞〜＜１２＞のいずれかに記載の含フッ素重合体を必須成分とする表面処理剤。
＜１４＞
表面処理剤が、撥水撥油剤、防汚剤または汚れ脱離剤である＜１３＞に記載の表面処理剤。 <12>
The fluorine-containing polymer according to any one of <1> to <11>, wherein the amount of the acrylate ester monomer (b) is 5 to 300 parts by weight with respect to 100 parts by weight of the fluorine-containing monomer (a). .
<13>
<1>-<12> The surface treating agent which uses the fluorine-containing polymer in any one of <12> as an essential component.
<14>
<13> The surface treatment agent according to <13>, wherein the surface treatment agent is a water / oil repellent agent, an antifouling agent or a soil release agent.

＜１５＞
水性媒体をも含有する＜１３＞または＜１４＞に記載の表面処理剤。
＜１６＞
＜１３＞に記載の表面処理剤で処理することからなる、基材を処理する方法。
＜１７＞
＜１３＞に記載の表面処理剤によって処理された基材。 <15>
The surface treating agent according to <13> or <14>, which also contains an aqueous medium.
<16>
<13> The method to process a base material consisting of processing with the surface treating agent as described in.
<17>
The base material processed with the surface treating agent as described in <13>.

Claims (15)

（ａ）α位が一価の有機基またはハロゲン原子で置換されているアクリレートエステル単量体である、フルオロアルキル基を有する含フッ素単量体から誘導された繰り返し単位、
（ｂ）アルキル基の炭素数が６〜１３であるアルキルアクリレートである非フッ素単量体から誘導された繰り返し単位、および
（ｃ）環状炭化水素基を有する非フッ素（メタ）アクリレート単量体から誘導された繰り返し単位
を有してなる含フッ素重合体。 (A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group, which is an acrylate ester monomer substituted at the α-position with a monovalent organic group or a halogen atom,
(B) a repeating unit derived from a non-fluorine monomer which is an alkyl acrylate having 6 to 13 carbon atoms in the alkyl group, and (c) a non-fluorine (meth) acrylate monomer having a cyclic hydrocarbon group A fluorine-containing polymer having a derived repeating unit. 含フッ素単量体（ａ）が、式：
CH2=C(−X)−C(=O)−Y−Z−Rf （Ｉ）
［式中、Ｘは、炭素数２〜２１の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ1Ｘ2基（但し、Ｘ1およびＸ2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基であり；
Ｙは、−Ｏ−または−ＮＨ−であり；
Ｚは、炭素数１〜１０の脂肪族基、炭素数６〜１８の芳香族基または環状脂肪族基、
-CH2CH2N(R1)SO2−基（但し、R1は炭素数１〜４のアルキル基である。）、
-CH2CH(OZ1)CH2-(Ph-O)p-基（但し、Z1は水素原子またはアセチル基、Phはフェニレン基、ｐは０または１である。）、-(CH2)n-Ph-O-基（但し、Phはフェニレン基、ｎは０〜１０である。）、-(CH2)m−SO2−(CH2)n−基または -(CH2)m−S−(CH2)n−基（但し、mは１〜１０、nは０〜１０である）、
Ｒｆは、炭素数１〜２０の直鎖状または分岐状のフルオロアルキル基である。]
で示される化合物である請求項１に記載の含フッ素重合体。 The fluorine-containing monomer (a) has the formula:
CH 2 = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where X 1 and X 2 are A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, substituted or non-substituted A substituted phenyl group;
Y is —O— or —NH—;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms),
-CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (where Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH 2 ) n -Ph-O-group (where, Ph is a phenylene radical, n is 0~10), -. (CH 2 ) m -SO 2 - (CH 2) n - group or - (CH 2) m -S- (CH 2) n - group (where, m is 1 to 10, n is 0-10),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
The fluorine-containing polymer according to claim 1, which is a compound represented by the formula: 含フッ素単量体（ａ）が、α位が塩素原子で置換されているアルキルアクリレートである請求項１または２に記載の含フッ素重合体。   The fluorine-containing polymer according to claim 1 or 2, wherein the fluorine-containing monomer (a) is an alkyl acrylate substituted at the α-position with a chlorine atom. 含フッ素単量体（ａ）において、Rfの炭素数が１〜６である請求項２または３に記載の含フッ素重合体。   The fluorine-containing polymer according to claim 2 or 3, wherein in the fluorine-containing monomer (a), Rf has 1 to 6 carbon atoms. アルキルアクリレート（ｂ）が、式：
ＣＨ２＝ＣＡ１ＣＯＯＡ２
［式中、Ａ１は、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ａ２は、ＣｎＨ２ｎ＋１（ｎ＝６〜１３）によって表されるアルキル基である。］
で示されるアルキルアクリレートである請求項１〜４のいずれかに記載の含フッ素重合体。 The alkyl acrylate (b) has the formula:
CH 2 = CA 1 COOA 2
[Wherein, A 1 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A 2 is an alkyl group represented by C n H 2n + 1 (n = 6 to 13). ]
The fluorine-containing polymer according to any one of claims 1 to 4, which is an alkyl acrylate represented by the formula: アルキルアクリレート単量体（ｂ）が、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレートおよびトリデシル（メタ）アクリレートからなる群から選択された少なくとも１種である請求項１〜５のいずれかに記載の含フッ素重合体。   The alkyl acrylate monomer (b) is hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) The fluorine-containing polymer according to any one of claims 1 to 5, which is at least one selected from the group consisting of acrylate and tridecyl (meth) acrylate. 環状炭化水素基を有する非フッ素（メタ）アクリレート単量体（ｃ）が、式：
ＣＨ２＝ＣＡ−Ｃ(＝Ｏ)−Ｏ−Ｑ
［式中、Ａは、水素原子、メチル基、または、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Ｑは、環状炭化水素基である。］
で示される化合物である請求項１〜６のいずれかに記載の含フッ素重合体。 The non-fluorine (meth) acrylate monomer (c) having a cyclic hydrocarbon group has the formula:
CH 2 = CA-C (= O) -O-Q
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
Q is a cyclic hydrocarbon group. ]
The fluorine-containing polymer according to any one of claims 1 to 6, which is a compound represented by the formula: 含フッ素重合体が、さらに、
（ｄ）ハロゲン化オレフィン単量体から誘導された繰り返し単位、および
（ｅ）単量体（ｂ）および（ｄ）以外の非フッ素単量体から誘導された繰り返し単位
からなる群から選択された少なくとも１種の繰り返し単位を有する請求項１〜７のいずれかに記載の含フッ素重合体。 The fluorine-containing polymer is further
(D) selected from the group consisting of repeating units derived from halogenated olefin monomers and (e) repeating units derived from non-fluorine monomers other than monomers (b) and (d) The fluorine-containing polymer according to any one of claims 1 to 7, which has at least one repeating unit. ハロゲン化オレフィン単量体（ｄ）が、１〜１０の塩素原子、臭素原子またはヨウ素原子で置換されている炭素数２〜２０のオレフィンである請求項８に記載の含フッ素重合体。   The fluorine-containing polymer according to claim 8, wherein the halogenated olefin monomer (d) is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. 含フッ素単量体（ａ）１００重量部に対して、アクリレートエステル単量体（ｂ）の量が５〜３００重量部であり、非フッ素アクリレート単量体（ｃ）の量が０．１〜８００重量部である請求項１〜９のいずれかに記載の含フッ素重合体。   The amount of the acrylate ester monomer (b) is 5 to 300 parts by weight and the amount of the non-fluorine acrylate monomer (c) is 0.1 to 100 parts by weight of the fluorine-containing monomer (a). It is 800 weight part, The fluorine-containing polymer in any one of Claims 1-9. 請求項１〜１０のいずれかに記載の含フッ素重合体を必須成分とする表面処理剤。   The surface treating agent which uses the fluoropolymer in any one of Claims 1-10 as an essential component. 表面処理剤が、撥水撥油剤、防汚剤または汚れ脱離剤である請求項１１に記載の表面処理剤。   The surface treating agent according to claim 11, wherein the surface treating agent is a water / oil repellent, an antifouling agent or a soil release agent. 水性媒体をも含有する請求項１１または１２に記載の表面処理剤。   The surface treating agent according to claim 11 or 12, which also contains an aqueous medium. 請求項１１に記載の表面処理剤で処理することからなる、基材を処理する方法。   A method for treating a substrate, comprising treating with the surface treatment agent according to claim 11. 請求項１１に記載の表面処理剤によって処理された基材。   The base material processed with the surface treating agent of Claim 11.
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